Trichromatic dyeing process and dye mixtures used therein

ABSTRACT

The present invention relates to a process for the trichromatic dyeing or printing of hydroxy-group-containing or nitrogen-containing organic substrates with dye mixtures and also to such dye mixtures and hydroxy-group-containing or nitrogen-containing organic substrates dyed or printed therewith.

[0001] The present invention relates to a process for the trichromatic dyeing or printing hydroxy-group-containing or nitrogen-containing organic substrates with dye mixtures and also to such dye mixtures and hydroxy-group-containing or nitrogen-containing organic substrates dyed or printed therewith.

[0002] Trichromatic describes the additive colour mixing of suitable yellow- or orange-, red- and blue-dyeing dyes with which any desired shade in the visible spectrum can be obtained by suitably selecting the amount ratios for the dyes.

[0003] Trichromatic dyeing is well known from the literature for various dye classes, for example from EP 83299, DE 2623178, EP 226982 and EP808940.

[0004] Optimum trichromatic performance of any yellow (or orange), red and blue dye mixture is crucially dependent on the neutral affinity and migration characteristics. Dyes having identical or very similar characteristics with regard to neutral affinity and migration are highly compatible with regard to trichromatic performance.

[0005] It is an object of the present invention to provide a trichromatic dyeing process and associated trichromatic dye mixtures consisting of at least one red component, at least one yellow (or orange) component and at least one blue component whereby trichromatic dyeing with good fastnesses is obtained.

[0006] This object is achieved by a trichromatic dyeing process which is characterized by using a dye mixture comprising at least one red-dyeing compound of the formula (I)

[0007] wherein

[0008] R₁ is a C₁₋₄-alkyl group or a substituted C₂₋₄-alkyl group,

[0009] R₂ and R₃ are independently from each other H; —OH; —CN; C₁₋₂-alkyl; —SO₃H; —COOH; —OC₁₋₂-alkyl or —NH₂,

[0010] X is a halogen radical and

[0011] Y —CH═CH₂ or —CH₂CH₂-Z, wherein Z is a radical which can be eliminated by alkali,

[0012] and at least one yellow (or orange)-dyeing compound;

[0013] and at least one blue-dyeing compound.

[0014] Various auxiliaries, such as surface-active compounds, solubilising agents, thickeners, gel-forming substances, antioxidants, penetration agents, sequestering agents, buffers, light protection agents, care agents may additionally be present in the composition according to the invention.

[0015] Such auxiliaries are in particular wetting agents, antifoams, levelling agents, thickeners and plasticizers.

[0016] For the preparation of inks for printing processes suitable organic solvents or mixtures thereof are used. E.g. alcohols, ethers, esters, nitriles, carbonacidamides, cyclic amides, urea, sulfones and sulfone oxides.

[0017] Furthermore additional auxiliaries such as e.g. compounds, which adjust the viscosity and/or the surface tension, may be added to the ink composition.

[0018] Suitable yellow (or orange)-dyeing compounds for the inventive trichromatic process have the following formula (II)

[0019] wherein

[0020] R₄ and R₅ signify independently from each other H or —SO₃H,

[0021] A signifies a group of formula (i) or (ia)

[0022] wherein

[0023] X and Y have the same meanings as defined above,

[0024] R₆ and R₇ signify independently from each other H; unsubstituted C₁₋₄alkyl or substituted C₁₋₄alkyl,

[0025] B signifies

[0026] wherein R₈ C₁₋₄alkyl; —NH₂ or —NHC₁₋₄alkyl,

[0027] and the asterisk marks the bond to the —N═N— group.

[0028] Further suitable yellow (or orange)-dyeing compounds for the inventive trichromatic process have the following formula (111)

[0029] wherein

[0030] R₉ —SO₃H or —SO₂Y, wherein Y has the same definition as above,

[0031] R₁₀ H or —SO₃H,

[0032] R₁₁ H; unsubstituted C₁₋₄alkyl or substituted C₁₋₄alkyl,

[0033] D signifies

[0034] wherein

[0035] X and Y have the same meanings as defined above and

[0036] R₁₂ signifies H; unsubstituted C₁₋₄alkyl or substituted C₁₋₄alkyl.

[0037] Further suitable yellow (or orange)-dyeing compounds for the inventive trichromatic process have the following formula (IV)

[0038] wherein

[0039] R₁₃ H signifies; methyl; methoxy, ethoxy; —NHCONH₂ or —NHCOCH₃,

[0040] R₁₄ H signifies; methyl; methoxy or ethoxy,

[0041] RG signifies

[0042] wherein

[0043] R₁₅ signifies H or chlorine,

[0044] Y has the same definition as above and may be bonded in a meta- or in para-position with respect to the azo group.

[0045] Suitable blue-dyeing compounds for the inventive trichromatic process have the following formula (V)

[0046] wherein

[0047] R₁₆ signify H or —SO₃H and

[0048] R₁₇ signifies

[0049] wherein

[0050] X and Y have the same meanings as defined above,

[0051] R₁₈ and R₁₉ are independently from one another H; unsubstituted C₁-alkyl or substituted C₁₋₄alkyl,

[0052] n is 0 or 1,

[0053] T signifies

[0054] wherein

[0055] R₁₆ and Y have the meanings as defined above and

[0056] R₂₀ is H; unsubstituted C₁₋₄alkyl or substituted C₁₋₄alkyl.

[0057] Further suitable blue-dyeing compounds for the inventive trichromatic process have the following formula (VI)

[0058] in which

[0059] R₂₁ is H or —COOH,

[0060] each of R₂₂ and R₂₄ is independently H; —COOH; —SO₃H; —NHCOCH₃; —NHCOCHY₂—CH₂Y₁; —NHCOCY₂═CH₂ or —NHCOCH₂Y₁,

[0061] R₂₃—COOH,

[0062] Y₁ is chlorine; bromine; —OSO₃H or —SSO₃H and

[0063] Y₂ is H; chlorine or bromine.

[0064] Further suitable blue-dyeing compounds for the inventive trichromatic process have the following formula (VII)

[0065] in which

[0066] Y has the same meanings as defined above,

[0067] R₂₅ H or —SO₃H,

[0068] R₂₆ H or —SO₃H.

[0069] Further suitable blue-dyeing compounds for the inventive trichromatic process have the following formula (VIII)

[0070] wherein

[0071] each Y has independently from each other the same meanings as defined above

[0072] R₂₇ and R₂₈ are independently from each other H; unsubstituted C₁₋₄alkyl or substituted C₁₋₄alkyl.

[0073] A preferred trichromatic dyeing process is characterized by using a dye mixture comprising at least one red-dyeing compound of the formula (Ia)

[0074] wherein

[0075] X′ is Cl or F,

[0076] R′₁ is a C₁₋₂-alkyl, especially —C₂H₅, or a C₂₋₄-alkyl group, which is monosubstituted by Cl, F, Br, —OH, —CN or —NH₂,

[0077] R′₂ and R′₃ are independently from each other H; C₁₋₂-alkyl; —SO₃H or —OC₁₋₂alkyl, especially H; —CH₃; —SO₃H or —OCH₃ and

[0078] the —SO₂Y group is attached to the phenylring at position 3, 4 or 5, wherein Y is as defined above and

[0079] at least one yellow (or orange)-dyeing compound of the formula (II), (III) and/or (IV) and

[0080] at least one blue-dyeing compound as per the formula (V), (VI), (VII) and/or (VIII).

[0081] A more preferred trichromatic dyeing process is characterized by using a dye mixture comprising at least one yellow (or orange)-dyeing compound of formula (IIa), (IIb) and/or (IIc)

[0082] wherein A is

[0083] and/or at least one yellow (or orange)-dyeing compounds of formula (IIIa) or (IIIb)

[0084] wherein D is

[0085] and/or at least one yellow (or orange)-dyeing compounds of formula (IVa) or (IVb)

[0086] wherein RG is or

[0087] A more preferred trichromatic dyeing process is characterized by using a dye mixture comprising and/or at least one blue-dyeing compound of formula (Va), (Vb), (Vc), (Vd), (Ve) and/or (Vf)

[0088] wherein T is

[0089] and/or at least one blue-dyeing compounds of formula (VIa) or (VIb)

[0090] and/or at least one blue-dyeing compounds of formula (VIIa) or (VIIb)

[0091] and/or at least one blue-dyeing compound of formula (VIIIa)

[0092] It is to be noted that all compounds may also be present in salt form. Useful salts include in particular alkali metal, alkaline earth metal or ammonium salts or the salts of an organic amine.

[0093] It is likewise to be noted that the alkyl groups can be linear or branched.

[0094] Preferred hydroxy-group-containing or nitrogen-containing organic substrates are leather and fibrous materials, which comprise natural or synthetic polyamides and, particularly, natural or regenerated cellulose such as, cotton, viscose and spun rayon. The most preferred substrates are textile materials comprising cotton.

[0095] Compounds of the formula (I) are prepared by reacting a diazotized compound of the formula (1)

[0096] wherein all substituents have the meanings as defined above,

[0097] with a compound of the formula (2)

[0098] wherein all substituents have the meanings as defined above.

[0099] The process is preferably carried out in an aqueous medium at a temperature of from 0 to 40° C., more preferably 0 to 25° C. and at a pH of between 1 to 7, more preferably 1 to 6.

[0100] A dyestuff of formula (I) may be isolated in accordance with known methods, for example by salting out, filtering and drying optionally in vacuum and at slightly elevated temperature.

[0101] The yellow (or orange)-dyeing compounds are known from the state of the art and can therefore be produced according to the process given in the prior art. E.g. WO9963995, WO9963055 and F.Lehr, Dyes Pigm. (1990), 14(4), 257.

[0102] The blue-dyeing compounds are also known from the state of the art and can therefore be produced according to the process given in the prior art. E.g. EP 99721, EP84314, WO0168775, EP 149170, EP497174 and DE4241918.

[0103] This invention further provides dye mixtures for the trichromatic dyeing or printing of hydroxy-group-containing or nitrogen-containing organic substrates are used in the above processes according to the invention.

[0104] The inventive process for trichromatic dyeing or printing can be applied to all customary and known dyeing and printing processes, for example the continuous process, the exhaust process, the foam dyeing process and the ink-jet process.

[0105] The composition of the individual dye components in the trichromatic dye mixture used in the process according to the invention depends on the desired hue. For instance, a brown hue preferably utilizes 30-65% by weight of the yellow (or orange) component according to the invention, 10-30% by weight of the red component according to the invention and 10-30% by weight of the blue component according to the invention.

[0106] The red component, as described above, can consist of a single component or of a mixture of different red individual components.

[0107] The same applies to the yellow (or orange) and blue components.

[0108] The total amount of dyes in the process according to the invention is between 0.01 and 15% by weight, preferably between 1 and 10% by weight.

[0109] The present invention further provides hydroxy-group-containing or nitrogen-containing organic substrates dyed or printed by a dye mixture according to the invention.

[0110] The process according to the invention provides dyeings and prints having a homogeneous hue build-up throughout the entire hue spectrum with on-tone exhaustion, with a high bath exhaustion even in the case of fibres with low saturation and with a high dye build-up on fine fibres, particularly on microfibres.

[0111] The resulting dyeings or prints are notable for very high wet fastnesses, specifically the fastnesses in washing, perspiration and water. These good wet and fabrication fastnesses, which are in no way inferior to the fastness level of dyeings and prints with metal complexes, are obtained without aftertreatment. With an additional aftertreatment these fastnesses are even exceeded.

[0112] These excellent results are provided by metal-free elements which meet the current and future ecological requirements of national institutes and regulations.

[0113] The tables which follow show some examples of the individual components of the dye mixtures which are used in the inventive trichromatic dyeing process. TABLE 1 Examples 1-18 Examples of red-dyeing compounds of formula (Ib) according to formula (I) (Ib)

Position Position of Ex. of —O₂S— —SO₃H R₁ R₂ R₃ X 1 3 4 —CH₂CH₃ H H Cl 2 3 3 —CH₂CH₃ H H F 3 4 3 —CH₂CH₃ H H F 4 4 3 —CH₂CH₃ H H Cl 5 4 4 —CH₂CH₃ H H Cl 6 4 4 —CH₂CH₃ H H F 7 4 3 —CH₃ H H F 8 3 3 —CH₃ H H F 9 5 3 —CH₂CH₃ (2)-OCH₃ H Cl 10 4 3 —CH₂CH₃ (2)-OCH₃ (5)-CH₃ Cl 11 4 3 —CH₃ (2)-OCH₃ (5)-OCH₃ F 12 4 4 —CH₂CH₃ (2)-OCH₃ (5)-OCH₃ Cl 13 4 4 —CH₂CH₃ (2)-SO₃H H Cl 14 5 3 —CH₃ (2)-SO₃H H F 15 5 3 —CH₂CH₃ (2)-SO₃H H Cl 16 4 3 —CH₂CH₃ (2)-SO₃H H Cl 17 4 3 —CH₂CH₃ (2)-SO₃H H F 18 3 3 —CH₂CH₃ (4)-OCH₃ H Cl

[0114] TABLE 2 Examples 19-35 Examples of red-dyeing compounds of formula (Ic) according to formula (I) (Ic)

Position Position of Ex. of —O₂S— —SO₃H R₁ R₂ R₃ X 19 3 4 —CH₂CH₃ H H Cl 20 3 3 —CH₂CH₃ H H F 21 4 3 —CH₂CH₃ H H F 22 4 3 —CH₂CH₃ H H Cl 23 4 4 —CH₂CH₃ H H Cl 24 4 4 —CH₂CH₃ H H F 25 4 3 —CH₃ H H F 26 3 3 —CH₃ H H F 27 5 3 —CH₂CH₃ (2)-OCH₃ H Cl 28 4 3 —CH₂CH₃ (2)-OCH₃ (5)-CH₃ Cl 29 4 3 —CH₃ (2)-OCH₃ (5)-OCH₃ F 30 4 4 —CH₂CH₃ (2)-OCH₃ (5)-OCH₃ Cl 31 4 4 —CH₂CH₃ (2)-SO₃H H Cl 32 5 3 —CH₃ (2)-SO₃H H F 33 5 3 —CH₂CH₃ (2)-SO₃H H Cl 34 4 3 —CH₂CH₃ (2)-SO₃H H Cl 35 4 3 —CH₂CH₃ (2)-SO₃H H F

[0115] TABLE 3 Examples 36-52 Examples of mixtures of red-dyeing compounds of formula (Ib), (Ic), (Id) and (Ie) according to formula (I) (Ib)

(Ic)

(Id)

+ (Ie)

Position Position of Ex. of —O₂S— —SO₃H R₁ R₂ R₃ X 36 3 4 —CH₂CH₃ H H Cl 37 3 3 —CH₂CH₃ H H F 38 4 3 —CH₂CH₃ H H F 39 4 3 —CH₂CH₃ H H Cl 40 4 4 —CH₂CH₃ H H Cl 41 4 4 —CH₂CH₃ H H F 42 4 3 —CH₃ H H F 43 3 3 —CH₃ H H F 44 5 3 —CH₂CH₃ (2)-OCH₃ H Cl 45 4 3 —CH₂CH₃ (2)-OCH₃ (5)-CH₃ Cl 46 4 3 —CH₃ (2)-OCH₃ (5)-OCH₃ F 47 4 4 —CH₂CH₃ (2)-OCH₃ (5)-OCH₃ Cl 48 4 4 —CH₂CH₃ (2)-SO₃H H Cl 49 5 3 —CH₃ (2)-SO₃H H F 50 5 3 —CH₂CH₃ (2)-SO₃H H Cl 51 4 3 —CH₂CH₃ (2)-SO₃H H Cl 52 4 3 —CH₂CH₃ (2)-SO₃H H F

[0116] TABLE 4 Examples 53-56 Examples of yellow (or orange)-dyeing compounds of formula (II′) according to formula (II) (II′)

Position Ex. R₄ R₅ A —N═N— 53 SO₃H (3)-SO₃H

2 54 SO₃H (3)-SO₃H

2 55 H (4)-SO₃H

3 56 SO₃H (3)-SO₃H

2

[0117] TABLE 5 Examples 57-59 Examples of orange-dyeing compounds of formula (III′) according to formula (III) (III′)

Ex. R₉ R₁₀ D 57 —SO₃H H

58 SO₂CH₂CH₂OSO₃H SO₃H

59 SO₂CH₂CH₂OSO₃H SO₃H

[0118] TABLE 6 Examples 60-62 Examples of yellow (or orange)-dyeing compounds of formula (IV′) ac- cording to formula (IV) (IV′)

Position Ex. —SO₂CH₂CH₂OSO₃H G RG′ 60 4 —NH₂

61 3 —CH₃

62 4 —CH₃

[0119] TABLE 7 Examples 63-72 Examples of blue-dyeing compounds of formula (V) (V)

Ex. R₁₇ R₁₆ T 63 (4)-SO₂CH₂CH₂OSO₃H H

64 (4)-SO₂CH₂CH₂OSO₃H H

65 (5)-SO₂CH₂CH₂OSO₃H —SO₃H

66

(5)- —SO₃H

67

(5)- —SO₃H

68

(5)- —SO₃H

69

(5)- —SO₃H

70

(5)- —SO₃H

71

(5)- —SO₃H

72

(5)- -SO₃H

[0120] The application examples hereinbelow serve to illustrate the present invention. Parts are by weight and temperatures are in degrees Celsius, unless otherwise indicated.

APPLICATION EXAMPLE 1

[0121] A 20 g sample of bleached cotton knitting. is transferred in a solution of 16 g sodium sulfate in 200 ml water at 60° C.,

[0122] 0.5% (calculated on the fabric weight) of a red dye as per Example 1

[0123] 0.8% of a yellow dye as per Example 55

[0124] 0.5% of a blue dye as per Formula VIa and

[0125] portions of 0.3, 0.7 and 1 g of sodium carbonate are added at 60° C. after 30, 45 respectively 60 minutes. The temperature is maintained during another 60 minutes.

[0126] The dyed fabric is rinsed in hot distilled water during 2 minutes and in hot tap water during 1 minute. After being kept in 1000 ml distilled water at the boil for 20 minutes. the fabric is dried. It provides a brown cotton dyeing having good fastnesses.

EXAMPLES 2-6

[0127] These examples are made analogous to Use Example 1, but by using dyestuff mixtures as mentioned below. The resulted shade is given in brackets.

APPLICATION EXAMPLE 2 (olive shade)

[0128] 0.2% of a red dye as per Example 1

[0129] 0.4% of a yellow dye as per Example 55

[0130] 0.6% of a blue dye as per Formula VIa

APPLICATION EXAMPLE 3 (brown shade)

[0131] 0.3% of a red dye as per Example 39

[0132] 0.9% of a orange dye as per Example 60

[0133] 0.6% of a blue dye as per Formula Via

APPLICATION EXAMPLE 4 (olive shade)

[0134] 0.1% of a red dye as per Example 39

[0135] 0.5% of a yellow dye as per Example 60

[0136] 0.6% of a blue dye as per Formula VIa

APPLICATION EXAMPLE 5 (brown shade)

[0137] 0.5% of a red dye as per Example 2

[0138] 0.9% of a yellow dye as per Example 55

[0139] 0.3% of a blue dye as per Example 69

APPLICATION EXAMPLE 6 (olive shade)

[0140] 0.2% of a red dye as per Example 2

[0141] 0.4% of a yellow dye as per Example 55

[0142] 0.3% of a blue dye as per Example 69. 

1. Trichromatic coloring process for coloring a hydroxy-group-containing or nitrogen-containing organic substrates substrate comprising the step of coloring the substrate with a dye mixture comprising at least one red-dyeing compound of the formula (I)

wherein R₁ is a C₁₋₄-alkyl group or a substituted C₂₋₄-alkyl group, R₂ and R₃ are independently from each other H; —OH; —CN; C₁₋₂-alkyl; —SO₃H; —COOH; —OC₁₋₂-alkyl or —NH₂, X is a halogen radical and Y is —CH═CH₂ or —CH₂CH₂-Z, wherein Z is a radical which is eliminated by alkali, and at least one yellow or orange-dyeing compound and at least one blue-dyeing compound.
 2. Trichromatic coloring process according to claim 1, wherein the dye mixture comprises at least one yellow or orange-dyeing compound selected from the group consisting of formula (II)

wherein R₄ and R₅ independently from each other are H or —SO₃H, A is a group of formula (i) or (ia)

wherein X and Y have the same meanings as defined in claim 1, R₆ and R₇ independently from each other are H; unsubstituted C₁₋₄alkyl or substituted C₁₋₄alkyl, B is

wherein R₈ is C₁₋₄alkyl; —NH₂ or —NHC₁₋₄alkyl, and the asterisk marks the bond to the —N═N— group; of formula (III)

wherein R₉ is —SO₃H or —SO₂Y, wherein Y has the same definition as defined in claim 1, R₁₀ is H or —SO₃H, R₁₁ is H; unsubstituted C₁₋₄alkyl or substituted C₁₋₄alkyl, D is

wherein X and Y have the same meanings as defined in claim 1 and R₁₂ is H; unsubstituted C₁₋₄alkyl or substituted C₁₋₄alkyl; and formula (IV)

wherein R₁₃ is H; methyl; methoxy, ethoxy; —NHCONH₂ or —NHCOCH₃, R₁₄ is H; methyl; methoxy or ethoxy, RG is

wherein R₁₅ is H or chlorine, Y has the same definition as defined in claim
 1. 3. Trichromatic coloring process according to claim 1, wherein the dye mixture comprises at least one blue-dyeing compound selected from the group consisting of formula (V)

wherein R₁₆ is H or —SO₃H, R₁₇ is

wherein X and Y have the same meanings as defined in claim 1, R₁₈ and R₁₉ are independently from one another H; unsubstituted C₁₋₄alkyl or substituted C₁₋₄alkyl, n is 0 or 1, T is

wherein R₁₆ has the meanings as defined above and Y has the meanings as defined in claim 1 and R₂₀ is H; unsubstituted C₁₋₄alkyl or substituted C₁₋₄alkyl; formula (VI)

in which R₂₁ is H or —COOH, each of R₂₂ and R₂₄ is independently H; —COOH; —SO₃H; —NHCOCH₃; —NHCOCHY₂—CH₂Y₁; —NHCOCY₂═CH₂ or —NHCOCH₂Y₁, R₂₃ is —COOH, Y₁ is chlorine; bromine; —OSO₃H or —SSO₃H and Y₂ is H; chlorine or bromine; formula (VII)

in which Y has the same meaning as defined in claim 1, R₂₅ is H or —SO₃H, R₂₆ is H or —SO₃H; and formula (VIII)

wherein each Y has independently from each other the same meanings meaning as defined in claim 1 R₂₇ and R₂₈ are independently from each other H; unsubstituted C₁₋₄alkyl or substituted C₁₋₄alkyl.
 4. Trichromatic coloring process according to claim 1, wherein the dye mixture comprises at least one red-dyeing compound of the formula (Ia)

wherein X′ is Cl or F, R′₁ is a C₁₋₂-alkyl, or a C₂₋₄-alkyl group, which is monosubstituted by Cl, F, Br, —OH, —CN or —NH₂, R₁₂ and R₁₃ are independently from each other H; C₁₋₂-alkyl; —SO₃H or —OC₁₋₂alkyl, —CH₃; —SO₃H or —OCH₃ and the —SO₂Y group is attached to the phenylring at position 3, 4 or 5, wherein Y is as defined in claim
 1. 5. Trichromatic coloring process according to claim 1, wherein the dye mixture comprises at least one yellow or orange-dyeing compound selected from the group consisting of formula (IIa), (IIb), (IIc)

wherein A is

formula (IIIa) (IIIb)

wherein D is

formula (IVa) and (IVb)

wherein RG is


6. Trichromatic coloring process according to claim 1 wherein the dye mixture comprises at least one blue-dyeing compound selected from the group consisting of formula (Va), (Vb), (Vc), (Vd), (Ve) (Vf)

wherein T is

formula (VIa) (VIb)

formula (VIIa) (VIIb)

(VIIa) (VIIb) and formula (Villa)


7. (Cancelled)
 8. A hydroxy-group-containing or nitrogen-containing organic substrate colored by a trichromatic coloring process as claimed in claim
 1. 9. Trichromatic coloring process according to claim 1, wherein the coloring step further comprises the step of dyeing or printing the substrate.
 10. Trichromatic coloring process according to claim 2, Y is bonded in a meta or para position with respect to the azo group.
 11. A dye mixture comprising: at least one red-dyeing compound of the formula (I)

wherein R₁ is a C₁₋₄-alkyl group or a substituted C₂₋₄-alkyl group, R₂ and R₃ are independently from each other H; —OH; —CN; C₁₋₂-alkyl; —SO₃H; —COOH; —OC₁₋₂-alkyl or —NH₂, X is a halogen radical and Y is —CH═CH₂ or —CH₂CH₂-Z, wherein Z is a radical which is eliminated by alkali, and at least one yellow or orange-dyeing compound; and and at least one blue-dyeing compound. 